EP0512423A2 - Aqueous solutions of cationic polyamidoamine resins - Google Patents

Abstract

Aqueous resin solution containing, as resin, a water-dilutable polyamidoamine-epichlorohydrin resin (A) obtained by a) reacting a water-dilutable, basic polyamidoamine (B) with epichlorohydrin, b) reacting the resultant resin with an inorganic base and with a water-soluble organic monoamine or polyamine or with ammonia or mixtures thereof and c) adding an acid so that a pH of from 1 to 7 is achieved. b

Description

From German Auslegeschrift 11 77 824 it is known to react polyamines with at least three amino groups with C₃-C₁₀ dicarboxylic acids and to convert the polyamides thus obtained into water-soluble condensation products with epichlorohydrin. The epichlorohydrin can be used in a molar ratio to the secondary amino groups of the polyamide of about (0.5 to 1.8): 1. The products obtained can be used to improve the wet strength of paper. Products of this type are also from German laid-open documents 22 29 219, 22 57 271, 29 38 588, 29 49 870 and 37 08 544, German patent documents 17 20 905, 17 71 043 and 19 06 450, European patent applications 0 131 200 and 0 126 176 and U.S. Patents 29 26 154 and 33 32 901.

It is also known (for example from British Patent 865,727) that such aqueous condensation products, prepared from polyamidoamines and epichlorohydrin, contain, inter alia, chlorohydrin structural units. As a result, polyamidoamine-epichlorohydrin resins can have a significant proportion of organically bound chlorine. According to German Offenlegungsschrift 37 08 544, these halohydrin reactive groups are necessary in order to obtain sufficiently crosslinkable and storage-stable products.

The halohydrin group-containing resins have a high affinity for the hydrated cellulose due to their cationic charge, but do not adhere completely to the paper fiber when used as a wet strength agent. Depending on the application conditions, such as density and composition, parts of the products get into the wastewater and contribute to its contamination with organically bound chlorine. Due to environmental protection requirements, it is now necessary to provide paper resins with the lowest possible organically bound chlorine content.

European patent application 0 349 935 discloses storage-stable, aqueous resin solutions with a pH of at most 7, containing as resin a water-dilutable polyamidoamine-epichlorohydrin resin (A) obtained by converting a water-dilutable, basic polyamidoamine (B) consisting of an acid component (B₁), and an amine component (B₂), with epichlorohydrin, the content of organically bound chlorine in the resin (A) being at most 4% by weight and the component (B₂) - if the acid component (B₁) an aliphatic or aromatic carboxylic acid or its functional derivatives, optionally in a mixture with an amino carboxylic acid or its lactams - consists of a mixture of polyamines and alkanol monoamines.

From example 6 of European patent application 0 349 935 it can be seen that at pH 4 storage stable Products with an organically bound chlorine content of 2.8% based on resin (A) can be obtained. In contrast, in Example 8 of the same patent specification with a chlorine content of 1.0%, based on resin (A), acidification to pH 1.75 is necessary in order to achieve sufficient storage stability.

The low pH setting is undesirable in paper processing because larger amounts of alkali have to be used for neutralization. In addition, such strongly acidic resins show a relatively rapid drop in performance during storage.

However, the products according to European patent application 0 349 935 are only sufficiently stable at a pH of approx. 4 if they have an increased chlorine content (approx. 1.5%). With the products according to this state of the art, it is only ever possible to optimize two of these properties (pH of approx. 4, chlorine content below 1%, storage stability) at the expense of the third property.

The object of the invention was to meet all three requirements and to find cationic compounds which are stable in storage at pH values greater than 3 and which are on a par with common products according to the prior art in terms of their wet strength and at the same time are significantly less, i.e. less than 0, 8% based on resin (A), contains organically bound chlorine.

Surprisingly, it has now been found that the after-reaction according to the invention of compounds containing halohydrin groups treated with inorganic bases with a water-soluble aliphatic, cycloaliphatic or araliphatic mono- or polyamine with tertiary, secondary and optionally primary amino groups or ammonia or mixtures thereof and subsequent addition thereof from acid to a pH of at most 7 stable compounds which have considerably less organically bound chlorine and which have similarly high wet strength activities as the products according to the prior art.

• a) Umsetzung eines wasserverdünnbaren, basischen Polyamidoamins (B) mit Epichlorhydrin,
• b) Reaktion der so erhaltenen Harze mit einer anorganischen Base und mit einem wasserlöslichen organischen Mono- oder Polyamin oder mit Ammoniak oder deren Gemischen und
• c) Zugabe einer Säure, daß ein pH-Wert von 1 bis 7 erreicht wird.

The invention relates to aqueous resin solutions containing a water-dilutable polyamidoamine-epichlorohydrin resin (A) obtained by

• a) reaction of a water-dilutable, basic polyamidoamine (B) with epichlorohydrin,
• b) reaction of the resins thus obtained with an inorganic base and with a water-soluble organic mono- or polyamine or with ammonia or mixtures thereof and
• c) adding an acid so that a pH of 1 to 7 is reached.

The content of resin (A) in the solution according to the invention is generally between 8 and 25% by weight, preferably 10 and 15% by weight, based on the solution. In addition, this resin solution contains small amounts of inorganic Substances (from the base treatment and the subsequent neutralization) and optionally up to 0.5% by weight, preferably 0.05 to 0.2% by weight, of fungicidal agents, such as sorbic acid or potassium sorbate and, if appropriate, further additives, such as for example defoaming agents.

The resin (A) generally has an average molecular weight M _n of at least 500, preferably at least 1000 and in particular from 1000 to 300000. The content of organically bound chlorine is generally between 0.01 and 2.5, preferably between 0. 01 and 2 and in particular between 0.01 and 1 wt .-%. In a 12.5% resin solution, this chlorine content does not exceed 0.3% by weight and is generally between 0.001 and 0.3, preferably between 0.001 and 0.25 and in particular between 0.001 and 0.125% by weight to the solution.

The water-soluble polyamidoamine (B) generally has an average molecular weight M _n (determined via the carboxyl end groups) of at least 500, preferably at least 1000 and in particular 2000 to 20,000; the amine number is usually between 200 and 400, preferably between 250 and 350 mgKOH / g and the acid number between 0 and 50, preferably 10 and 30 mgKOH / g.

Polyamidoamines (B) which meet the conditions according to the invention are, for example, in DE-AS 17 77 824, GB-PS 865.727, US Pat. No. 4,075,177 and 4,336,835, DE-OS 33 23 732 and EP-OS 31 899, to which reference is made here.

The corresponding products according to DE-OS 33 23 732 are preferred insofar as they come under the present framework.

Generally, such polyamidoamines (B) are obtained by reacting an acid component (B₁), such as dicarboxylic acids or their functional derivatives, and ω-aminocarboxylic acids or their lactams with an amine component (B₂), such as polyamines, which may be present in a mixture with alkanolmonoamines. These polyamines contain at least two primary amino groups and preferably a secondary and / or tertiary amino group. The quantity ratio of the components is to be selected so that the resulting polyamidoamine (B) still has a sufficient number of basic (ie epichlorohydrin-reactive) amino groups, no gelling occurs during the reaction and the molecular weight of (A) in the range given lies.

• a) gesättigten oder olefinisch-ungesättigten aliphatischen C₃-C₁₀-Dicarbonsäuren oder deren funktionellen Derivaten bzw. mindestens 3 C-Atome enthaltenden ω-Aminocarbonsäuren oder deren Lactamen mit
• b1) aliphatischen Polyaminen, die mindestens zwei primäre und mindestens eine weitere, und zwar sekundäre und/oder tertiäre Aminogruppe enthalten, oder
• b2) einem Gemisch der Polyamine b1) mit
• c1) Polyaminen, die mindestens eine primäre und gegebenenfalls mindestens eine sekundäre Aminogruppe enthalten und nicht unter die Definition b1) fallen, wobei die zusätzlichen Polyamine in solchen Mengen verwendet werden können, daß deren Anteil an primären Aminogruppen, bezogen auf die Gesamtmenge der primären Aminogruppen, 70 %, vorzugsweise 50 % und insbesondere 30 %, nicht übersteigt, und/oder gegebenenfalls
• c2) Alkanolmonoaminen mit 2 bis 20 C-Atomen, vorzugsweise 2 bis 6 C-Atomen und 1 bis 3, vorzugsweise 1 oder 2 OH-Gruppen und insbesondere mit einer OH-Gruppe. Vorzugsweise besitzen diese Alkanolmonoamine die weiter unten angegebene Formel (II).

The polyamidoamines (B) are, for example, reaction products of

• a) saturated or olefinically unsaturated aliphatic C₃-C₁₀ dicarboxylic acids or their functional derivatives or ω-aminocarboxylic acids containing at least 3 carbon atoms or their lactams with
• b1) aliphatic polyamines which contain at least two primary and at least one further, namely secondary and / or tertiary amino group, or
• b2) with a mixture of the polyamines b1)
• c1) polyamines which contain at least one primary and optionally at least one secondary amino group and do not fall under definition b1), it being possible for the additional polyamines to be used in amounts such that their proportion of primary amino groups, based on the total amount of the primary amino groups, Does not exceed 70%, preferably 50% and in particular 30%, and / or if appropriate
• c2) Alkanol monoamines with 2 to 20 C atoms, preferably 2 to 6 C atoms and 1 to 3, preferably 1 or 2 OH groups and in particular with one OH group. These alkanol monoamines preferably have the formula (II) given below.

• 1. Umsetzungsprodukte von a) gesättigten aliphatischen C₃-C₁₀-Dicarbonsäuren, wie Bernsteinsäure, Glutarsäure, Adipinsäure, Sebazinsäure, Malonsäure oder deren funktionellen Derivaten, wie Anhydriden und Estern, wobei die drei erstgenannten Säuren bevorzugt sind, mit den vorstehend unter b) genannten Gemischen von Polyaminen mit Alkanolmonoaminen.
• 2. Umsetzungsprodukte von solchen gesättigten modifizierten Dicarbonsäuren bzw. deren Derivaten, die durch Anlagerung von aliphatischen, cycloaliphatischen, araliphatischen oder heterocyclischen Polyaminen, die mindestens zwei Aminogruppen und zwar primäre und/oder sekundäre enthalten an α,β-olefinisch-ungesättigte Carbonsäureester, deren Alkoholrest 1 bis 8, vorzugsweise 1 bis 3 C-Atomen hat, wie Acrylsäureethylester und Methacrylsäuremethylester, erhalten und dann mit den vorstehend unter b1)/c1) genannten Polyaminen bzw. deren Gemischen, gegebenenfalls in Abmischung mit Alkanolmonoaminen, umgesetzt werden.
• 3. Umsetzungsprodukte von mindestens drei Kohlenstoffatomen enthaltenden ω-Aminocarbonsäuren oder deren Lactamen, z. B. 6-Aminocapronsäure und 8-Aminocaprylsäure bzw. 6-Caprolactam und 8-Capryllactam, mit den vorstehend unter b) genannten Gemischen von Polyaminen mit Alkanolmonoaminen.
• 4. Umsetzungsprodukte von olefinisch ungesättigten Dicarbonsäuren, wie Maleinsäure oder Fumarsäure bzw. deren funktionellen Derivaten, wie Anhydriden oder Estern, mit den vorstehend unter b1)/c1) genannten Polyaminen bzw. deren Gemischen, gegebenenfalls in Abmischung mit Alkanolmonoaminen.
• 5. Solche Umsetzungsprodukte, denen außer den unter 1. genannten gesättigten, aliphatischen C₃-C₁₀-Dicarbonsäuren und den unter 4. genannten ungesättigten Dicarbonsäuren noch ω-Aminocarbonsäuren oder deren Lactame des unter 3. angeführten Typs und außer den unter b1) angeführten Polyaminen noch mindestens eine primäre und gegebenenfalls sekundäre Aminogruppe, also z. B. eine primäre oder eine sekundäre Aminogruppe, enthaltende aliphatische, cycloaliphatische, araliphatische oder heterocyclische Polyamine und Alkanolamine zugrunde liegen. Hierbei sind diejenigen Polyamidoamine zu bevorzugen, denen außer den vorstehend unter b1)/c1) genannten Polyaminen bzw. deren Gemischen, gegebenenfalls in Abmischung mit Alkanolmonoaminen und außer den gesättigten C₃-C₁₀-Dicarbonsäuren noch ω-Aminocarbonsäuren oder deren Lactame des unter 3. angeführten Typs zugrunde liegen.

The following are particularly suitable as water-soluble polyamidoamines (B):

• 1. reaction products of a) saturated aliphatic C₃-C₁₀ dicarboxylic acids, such as succinic acid, glutaric acid, adipic acid, sebacic acid, malonic acid or their functional derivatives, such as anhydrides and esters, the first three acids preferred are, with the mixtures of polyamines with alkanol monoamines mentioned under b).
• 2. Reaction products of such saturated modified dicarboxylic acids or their derivatives, which by addition of aliphatic, cycloaliphatic, araliphatic or heterocyclic polyamines, which contain at least two amino groups, primary and / or secondary to α, β-olefinically unsaturated carboxylic acid esters, the alcohol radical thereof Has 1 to 8, preferably 1 to 3 carbon atoms, such as ethyl acrylate and methyl methacrylate, obtained and then reacted with the polyamines mentioned above under b1) / c1) or mixtures thereof, optionally in a mixture with alkanol monoamines.
• 3. reaction products of at least three carbon atoms containing ω-aminocarboxylic acids or their lactams, for. B. 6-aminocaproic acid and 8-aminocaprylic acid or 6-caprolactam and 8-capryllactam, with the above-mentioned mixtures of polyamines with alkanol monoamines.
• 4. reaction products of olefinically unsaturated dicarboxylic acids, such as maleic acid or fumaric acid or their functional derivatives, such as anhydrides or esters, with the polyamines mentioned above under b1) / c1) or their mixtures, optionally in a mixture with alkanol monoamines.
• 5. Such reaction products which, in addition to the saturated, aliphatic C₃-C₁₀ dicarboxylic acids mentioned under 1. and the unsaturated dicarboxylic acids mentioned under 4. still ω-aminocarboxylic acids or their lactams of the type mentioned under 3. and except for the polyamines listed under b1) at least one primary and optionally secondary amino group, e.g. B. a primary or a secondary amino group containing aliphatic, cycloaliphatic, araliphatic or heterocyclic polyamines and alkanolamines. In this case, those polyamidoamines are preferred which, in addition to the polyamines mentioned above under b1) / c1) or their mixtures, optionally in a mixture with alkanol monoamines and in addition to the saturated C₃-C₁₀ dicarboxylic acids, ω-aminocarboxylic acids or their lactams mentioned under 3 Type.

Reaction products of type 1) using diethylene triamine, triethylene tetramine and tetraethylene pentamine as the polyamine and 2-aminoethanol as the alkanol monoamine are particularly preferred.

in Betracht, in der

p

Null oder eine ganze Zahl von 1 bis 6, vorzugsweise 1 bis 4 ist,

R₁

einen zweiwertigen, vorzugsweise nichtaromatischen Kohlenwasserstoffrest mit 2 bis 18 C-Atomen, vorzugsweise einen verzweigten oder unverzweigten Alkylenrest mit 2 bis 10 C-Atomen, insbesondere mit 2 bis 6 C-Atomen, oder einen Cycloalkylenrest mit 5 bis 12 C-Atomen, vorzugsweise 6 bis 10 C-Atomen, oder einen Aralkylenrest mit 7 bis 12 C-Atomen, vorzugsweise 8 bis 10 C-Atomen darstellt und R₂, R'₂ unabhängig voneinander für H oder einer der beiden Reste für



        R₁ - NR₃R₄

stehen, worin

R₁

die gleiche Bedeutung wie vorstehend hat und

R₃ und R₄

entweder unabhängig voneinander für H, (C₁-C₂₀)-Alkyl, vorzugsweise (C₁-C₆)-Alkyl, stehen, wobei diese Alkylreste auch Hydroxygruppen tragen können.

Examples of polyamines b1) and c1) are those of the formula (I)

considered in the

p

Is zero or an integer from 1 to 6, preferably 1 to 4,

R₁

a divalent, preferably non-aromatic hydrocarbon radical having 2 to 18 carbon atoms, preferably a branched or unbranched alkylene radical having 2 to 10 carbon atoms, in particular having 2 to 6 carbon atoms, or a cycloalkylene radical having 5 to 12 carbon atoms, preferably 6 represents up to 10 carbon atoms, or an aralkylene radical with 7 to 12 carbon atoms, preferably 8 to 10 carbon atoms and R₂, R'₂ independently of one another for H or one of the two radicals for



R₁ - NR₃R₄

stand in what

R₁

has the same meaning as above and

R₃ and R₄

either independently of one another represent H, (C₁-C₂₀) alkyl, preferably (C₁-C,) alkyl, these alkyl radicals also being able to carry hydroxyl groups.

As polyamines b1) z. B. called methyl bis (3-aminopropyl) amine, ethyl bis (3-aminopropyl) amine, N- (3-aminopropyl) tetramethylene diamine, N, N'-bis (3-aminopropyl) tetramethylene diamine, polyalkylene polyamines such as dipropylene (1,2) triamine, bis (3-aminopropyl) amine, Tripropylene (1,2) tetramine and especially diethylene triamine, triethylene tetramine and tetraethylene pentamine.

Polyamines c1) are, for example: ethylenediamine, propylenediamine, 1-amino-3-methylamino-propane, 2-methylpentamethylenediamine, pentamethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, neopentyldiamin, octamethylenediamine, dioxadodecanediamine, cycloaliphatic diamines, or 1,3-cycloaliphatic diamines , 4-cyclohexanediamine, 4,4'-methylene-bis-cyclohexylamine, isophoronediamine, menthandiamine, 4,4'-diamino-3,3'-dimethyl-di-cyclohexylmethane, 3-aminomethyl-1- (3-aminopropyl-1 -methyl) -4-methylcyclohexane, N-methylethylenediamine, N-aminoethylpiperazine, 1,3-bis-aminomethylbenzene.

Examples of alkanol monoamines are those of the formula



H₂N-R₁-OH (II)



suitable in which R₁ has the above meaning, such as 2-aminoethanol, 1-amino-2-propanol, 3-amino-1-propanol, 2-amino-1-butanol, 4-amino-1-butanol, 5-amino -1-pentanol, 6-amino-1-hexanol and their isomers, the hydrocarbon radical of which is branched or which carry the amino group and / or the hydroxyl group on a primary or secondary carbon atom; also those that differ from cyclic Derive hydrocarbon residues, preferably with 5-7 carbon atoms.

The quantitative ratios of the components in question to be maintained to achieve water-soluble polyamidoamines (B) with optimal properties can easily be determined by preliminary tests.

In general, the molar amount of dicarboxylic acid or its functional derivatives to polyamine / alkanol monoamine is such that the ratio of carboxyl groups to the sum of primary NH₂ groups is 1: (0.8-1.4), preferably 1: (0, 95 - 1.1). In the case of mixtures of polyamines and alkanol monoamines, the ratio of their molar amounts is 0.6: 0.4 to 0.99: 0.01, preferably 0.8: 0.2 to 0.95: 0.05.

The polyamidoamines (B) can be prepared in the customary manner, for. B. by heating the corresponding components for several hours with the exclusion of oxygen to temperatures of 125 to 250 ° C, preferably from 140 to 180 ° C, first under ordinary pressure and then under reduced pressure, with small amounts of hydrazine hydrate to avoid the darkening of the polyamides or hydrazides can be added. The reaction time depends on the temperatures and pressures used and is generally between 4 and 10 hours.

Instead of the epichlorohydrin, the dichlorohydrin (1,3-dichloro-2-hydroxypropane) can optionally also be used, preferably 1.0 to 1.4 mol per mol sec. basic amino groups. The ratio of the molar amount of epichlorohydrin to the sum of the equivalents of free basic amino groups in the polyamidoamine (B) is 0.6: 1 to 4: 1, preferably 1: 1 to 1.4: 1. Free basic amino groups are primary, secondary or to understand tertiary amino groups. For the term "equivalents" cf. Pure appl. Chem. 50 (1978), pp. 327-338, esp. P. 337.

The amount of base is 0.1 to 1.0 mol, preferably 0.1 to 0.6 mol, per mol of epichlorohydrin used. The amount of organic mono- or polyamines is 0.01 to 4, preferably 0.1 to 1, basic amine equivalents per mole of epichlorohydrin.

The following can be used as inorganic bases: alkali metal hydroxides, preferably sodium and potassium hydroxide, carbonates, bicarbonates, alkaline earth metal hydroxides such as calcium hydroxide, furthermore benzyltrimethylammonium hydroxide, tetramethylammonium hydroxide or corresponding mixtures.

Compounds of the formulas III or IV are preferably used as water-soluble organic mono- or polyamines for the after-reaction according to the invention



NR₁R₂R₃ (III) or R₄R₅N (-R-NR₈) _n -R-NR₆R₇ (IV)



question what
R is an aliphatic, cycloaliphatic or araliphatic alkylene or hydroxyalkylene radical having 1 to 300 carbon atoms, which can be interrupted by heteroatoms such as oxygen and sulfur, and R₁, R₂, R₃, R₄, R₅, R₆, R₇ independently of one another hydrogen or an aliphatic , Cycloaliphatic or araliphatic alkyl or hydroxylalkyl radical having 1 to 20 carbon atoms, which can be interrupted by heteroatoms such as oxygen and sulfur, and n is an integer from 0 to 10.

Tertiary monoamines of the formula III are, for example, the following compounds: trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tributylamine, NN-dimethylethylamine, N, N-dimethylisopropylamine, N, N-dimethylcyclohexylamine, benzyldimethylamine, benzyldiethylamine, N -Methylmorpholine, N-methylpiperidine, triethanolamine, dimethylethanolamine, diethylethanolamine, diisopropylethanolamine, dibutylethanolamine, methyldiethanolamine, butyldiethanolamine, triisopropanolamine, dimethylisopropanolamine, diethylisopropanolamine, dimethylpropanolamine, diethylisopropanolamine, dimethylisopropanolamine, methyldiethylisopropanolamine, methyldiisopropanolamine, dimethylethylaminophenamine, dimethyl propanolamine, dimethyl propanolamine, dimethyl propanol amine, dimethyl propanolamine, dimethyl propanolamine, dimethyl propanolamine, dimethyl propanolamine, dimethyl propanolamine, dimethyl propanolamine, dimethyl propanolamine, dimethyl propanolamine, dimethyl propanolamine, dimethyl propanolamine, dimethyl propanolamine, dimethyl propanolamine, dimethyl propanolamine, dimethyl propanolamine, dimethyl propanolamine, dimethyl propanolamine, dimethyl propanolamine, dimethyl propanolamine, dimethyl propanolamine, 1 : Dimethylamine, diethylamine, dipropylamine, diisopropylamine, di-n-butylamine, di-isobutylamine, di-sec-butylamine (N- (1-methylpropyl) -2-butanamine), di-n-pentylamine, di-hexylamine, Di-2-ethylhexylamine, Methyl-ethylamine, methyl-propylamine, methyl-butylamine, ethyl-isopropylamine, methyl-iso-butylamine, ethyl-butylamine, Nn-propyl-s-butylamine, di-2-methylbutylamine, N-methyl-cyclohexylamine, N-ethyl cyclohexylamine, N-butyl-cyclohexylamine, dicyclohexylamine, di-2-methoxyethylamine, diethanolamine, di-n-propanolamine, di-iso-propanolamine, N-methylethanolamine, N-ethylethanolamine, N-methylisopropanolamine, cyclohexylethanolamine, Morpholine, pyrrolidine, primary monoamines such as: methylamine, ethylamine, propylamine, isopropylamine, n-iso- and sec-butylamine, t-butylamine, n-pentylamine, 3-amino-pentane, 3-methyl-1-butanamine, 2 -Methyl-2-butanamine, n-hexylamine, 3-amino-3-methylpentane, 2-ethylhexylamine, 3-methyl-1-butanamine, 3-methyl-2-butanamine, 1-methyl-1-butanamine, 2-ethyl -1-butanamine, 2-methoxyethylamine, 2-ethoxyethylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3- (2-methoxyethoxy) propylamine, cyclopropanamine, cyclopentylamine, cyclohexylamine, 2-methylcyclohexylamine, 1- and 2- Phenylethylamine, Benzylamine, 4-methoxybenzylamine, 1-methyl-3-phenylpropylamine, 2-aminoethanol, 1-amino-2-propanol, 3-amino-1-propanol, 2-amino-1-butanol, 2-amino-3-pentanol, Polyhydroxymonoamines such as 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol and 2- (2-aminoethoxy) ethanol.

Polyamines of the formula IV are, for example, the following compounds: 1,4-diazabicyclo (2.2.2) octane, N, N, N ', N'-tetramethylethanediamine, N, N, N', N'-tetramethyl-1,3- propanediamine, N, N, N ', N'-tetramethyl-1,6-hexanediamine, N, N, N', N'-tetramethyldiaminodiethyl ether, N, N, N ', N'-pentamethyldiethylenetriamine, Ethylenediamine, N, N'-dimethyl-1,2-ethanediamine, N-methyl-1,2-ethanediamine, N-ethyl-1,2-ethanediamine, N, N-diethyl-1,2-ethanediamine, N- ( 2-hydroxyethyl) 1,2-ethanediamine, 1,2-diaminopropane, 1,3-diaminopropane, 2-hydroxy-1,3-diaminopropane, 3-amino-1-methylaminopropane, N, N-dimethyl-1,3- propanediamine, N, N'-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N-cyclohexyl-1,3-propanediamine, 2,2-dimethyl-1,3-propanediamine , 1,3-diaminobutane, 1,4-diaminobutane, 1,3-bis (2-hydroxyethylamino) propane, 1,4-bis-methylaminobutane, N, N-diethyl-1,4-pentanediamine, 2- Methyl-1,5-pentanediamine, 1,5-pentanediamine, 1,6-diaminohexane, 2,2,4- and 2,4,4-trimethyl-1,6-hexanediamine, 1,2-, 1,3- and 1,4-diaminocyclohexane, menthandiamine, piperazine, 3,5,5-trimethyl-3-aminomethylcyclohexylamine, (isophoronediamine), 4,4'-methylene-bis-cyclohexylamine, 4,4'-methylene-bis- ( 2-methylcyclohexylamine), bis (2-aminoethyl) ether, 2,2'-bis-methylaminodiethyl ether, bis (3-aminopropyl) ether, bis (3-aminopropyl) sulfide, 4.9- Dioxadodecane-1,12-diami n, 4,7,10-trioxatridecane-1,13-diamine, 1,3-bisaminomethylbenzene (m-xylylenediamine), TCD-diamine (bis (amino-methyl) tricyclodecane), diethylenetriamine, dipropylenetriamine, tetraethylenepentamine, pentaethylenehexamine, tripropylenetetramine, higher polyalkylene polyamines, methyl bis (3-aminopropyl) amine, dihexamethylenetriamine, aminoethylpiperazine, 3- (2-aminoethyl) aminopropylamine, N, N'-bis (3-aminopropyl) ethylenediamine, ethyl bis (3 -aminopropyl) -amine, 2-hydroxyethyl-bis- (3-aminopropyl) -amine, N- (3-aminopropyl) -tetramethylenediamine, N, N'-bis- (3-aminopropyl) -tetramethylene-diamine, 1,3-bis - (2-aminoethylamino) propane, 3- (3-diethylamino propylamino) propylamine, 2,2'-bis (2-aminoethylamino) diethyl ether, 1,6-bis (2-aminoethylamino) hexane, 1,6 -Bis (3-amino-propylamino) -hexane, bis- (6-amino-n-hexyl) amine, polyalkylene polyamines, polyethyleneimines or mixtures thereof.

Polyamidoamines are particularly suitable as polyamines in stage b). The same polyamidoamines are used as polyamidoamines, as previously mentioned and described as component (B).

The reaction products can be prepared by the process according to the invention in such a way that the polyamidoamines (B) and epichlorohydrin in a first reaction step at a concentration of the reactants of about 25 to 50, preferably 35 to 45% and at a temperature between 25 and 95 ° C, preferably 40 to 75 ° C, can react until the viscosity of a 40% solution (determined at 25 ° C) is about 100 to 600, preferably 200 to 400 mPa.s. This solution is then placed in a second reaction step with an aqueous solution of an inorganic base, which is generally present in an amount of 0.1 to 1.0, preferably 0.1 to 0.6, mol per mol of epichlorohydrin used, and with a water-soluble, organic mono- or polyamine with tertiary, secondary and optionally primary amino groups or ammonia or mixtures thereof at a concentration of the reactants of 10 to 50, preferably 15 to 30% and a temperature between 25 and 95 ° C., preferably 40 to 75 ° C until the viscosity of a 12.5% solution (determined at 25 ° C) 10 - 200 mPa.s, preferably 15 to 80 mPa.s. The pH in this second reaction step is greater than 8, preferably between 9 and 12. Then the mixture is expediently added to the mixture in order to terminate the action and to stabilize the self-crosslinking reaction products, so much acid or acid derivatives that the pH the aqueous solution is 1 to 7, preferably between 1.5 and 5, and adjusts the solids content of the reaction solution to 8 to 25% by weight by dilution with water.

In another, less preferred embodiment, acid can first be added to the solution during or after the reaction of polyamidoamine (B) and epichlorohydrin, and the pH can be adjusted to less than 7, preferably 1.5 and 5. Sufficient inorganic base and water-soluble organic mono- or polyamine are then added to this acidic reaction mixture such that the pH is higher than 8, preferably between 9 and 12, and this system is then used for a period of 0.5 to 8 hours, preferably 1 to 4 hours at a temperature of 25 to 95 ° C, preferably 40 to 70 ° C.

The mono- or polyamine can be added immediately after the addition of the inorganic base until shortly before the desired viscosity is reached or shortly before the acid is added. The addition of the mono- or polyamine in the middle of this reaction period is particularly preferred.

In special cases, the mono- or polyamine can also be added before the base is added. In this case, however, the addition of the epichlorohydrin to the polyamidoamine (A) must have been completed.

Halogen-free acids are in particular sulfuric, phosphoric or acetic acid, their anhydrides or acidic salts of these acids.

The resin solutions according to the invention - whereby the term solution also includes colloidal solutions - have an excellent storage stability, that is to say that no noticeable gelation or precipitation occurs during storage for at least three months at room temperature or at least 10 days at 50.degree.

As a result of the additional reaction with the water-soluble organic mono- or polyamines, the resins or resin solutions according to the invention have a considerably lower organically bound chlorine content than the previously known reaction products of polyamidoamine and epichlorohydrin and are therefore outstandingly suitable for reducing the organic chlorine content of waste water, of paper mills, among other things. The reaction products which have hitherto been used to improve the wet strength effectiveness of paper do not possess this valuable property to the same extent. Because of the high storage stability of the invention Resin solutions, their wet strength effectiveness remains constant even after months of storage.

With the help of the reaction products produced by the process according to the invention, the wet strength of paper - including paper made from unbleached cellulose - can be outstandingly improved. In some cases, depending on the type of paper or as desired, it is also possible to increase the absorbency.

It is noteworthy that the reaction products practically do not affect the whiteness of paper made from bleached pulp. It should also be mentioned that the speed at which the reaction products to be used according to the invention crosslink on the paper or in the pulp is high and that the reaction products are also used as retention aids for fillers used in papermaking, drainage aids to improve the papermaking speed and flocculants to remove fine particles Particles from dirty water, for example industrial waste water, can be used.

In order to increase the wet strength of paper according to the present invention, one can proceed, for example, by adding the resins in question in the form of aqueous solutions to the aqueous suspension of the paper raw material before processing into paper. The amounts of resin required to achieve the desired wet strength can be determined by preliminary tests determine without difficulty. In general, it is advisable to use 0.05 to 2, preferably 0.1 to 1.6 parts by weight of solid resin per 100 parts by weight of paper stock, advantageously in the form of an aqueous solution, the content of reaction products of which is preferably 8 to 25 10 to 15 wt .-% is.

The following examples are intended to illustrate the invention in more detail. Unless otherwise stated, percent means percentages by weight. The organic chlorine content was determined from the difference between the chlorine content and the ionic chlorine content determined using the Wickbold combustion method (reference specifications: DIN 53 188, paragraph 13 and DIN 53 474, paragraph 5.5; 6.3).

Preparation of the polyamidoamines (B) example 1

392 g of diethylenetriamine (3.8 mol) and 24.4 g (0.4 mol) of 2-aminoethanol were placed in a four-necked flask equipped with a stirrer, thermometer and distillation apparatus, and 584 g of adipic acid ( 4 mol) was added in portions so that the temperature did not rise above 100.degree. The mixture was then heated to 150.degree. C. under nitrogen in 3 hours, held at this temperature for one hour and further heated to 170.degree. C., the water formed distilling out uniformly. After a holding time of about 2 hours, the reaction product had an acid number of 20 mgKOH / g and an amine number of 251 mgKOH / g. After removing the heater, the polyamidoamine was diluted with 570 g of water. The solution had a solids content of 59.8% (1 g, 1 hour at 125 ° C.) and a viscosity at 25 ° C. of 1174 mPa.s.

Example 2

546 g of diethylenetriamine (5.29 mol), 147 g of ethylenediamine (2.45 mol) and 50 g of 2-aminoethanol (0.82 mol) were placed in a four-necked flask equipped with a stirrer, thermometer and distillation apparatus, and within 1190 g of adipic acid (8.15 mol) were added in portions in the course of 2 hours so that the temperature did not rise above 100.degree. 461 g of caprolactam (4.07 mol) were then added over the course of 15 minutes, heated to 150 ° C. in 3 hours under nitrogen, held at this temperature for one hour and further heated to 170 ° C., the water formed distilling out uniformly. After a holding time of 2.5 hours, the reaction product had an acid number of 26 mgKOH / g and an amine number of 161 mgKOH / g. After the heater was removed, the polyamidoamine was diluted with 1400 g of water. The solution had a solids content of 61.7% (1 g, 1 hour at 125 ° C.) and a viscosity of 869 mPa.s.

Example 3

700 g of diethylenetriamine (6.78 mol), 188 g of ethylenediamine (3.13 mol) and 64 g of 2-aminoethanol (1.05 mol) were placed in a four-necked flask equipped with a stirrer, thermometer and distillation apparatus, and within 1524 g of adipic acid (10.43 mol) were added a little at a time so that the temperature did not rise above 100.degree. The mixture was then heated to 150 ° C. in the course of 3 hours, held at this temperature for one hour and further heated to 170 ° C., the water formed distilling out uniformly. After a holding time of 2 hours, the reaction product had an acid number of 23 mgKOH / g and an amine number of 204 mgKOH / g. After removing the heater, the polyamidoamine was diluted with 1400 g of water. The solution had a solids content of 61.3% (1 g, 1 hour at 125 ° C.) and a viscosity at 25 ° C. of 874 mPa.s.

Example 4

The polyamidoamine was prepared analogously to Example 3.

The dilution with water was carried out to a solids content (LC) of 29.9% (1 g, 1 hour at 125 ° C.).

The resin solution had an acid number of 26 mgKOH / g (on LC), an amine number of 201 mgKOH / g (on LC) and a viscosity at 25 ° C of 24 mPa.s.

Preparation of the polyamidoamine-epichlorohydrin resins (comparative examples without additional treatment with an amine) Example 5 (corresponds to example 6 of EP-0 349 935)

• a) 207 g of the polyamidoamine precursor solution from Example 1 (corresponding to 0.552 Val NH) and 207 g of water were placed in a three-necked flask equipped with a stirrer, thermometer and condenser and 66.5 g of epichlorohydrin (0.72 mol) were added with stirring. The mixture was heated to 60 ° C. in 45 min and held at this temperature. After 3.5 hours the Gardner viscosity had reached N.
• b) 578 g of 1% sodium hydroxide solution were added, heated to 65 ° C. and kept at this temperature. After 3 hours the Gardner viscosity was E-F. Then 442 g of water, in which 1.5 g of potassium sorbate were dissolved, were added, cooled and then adjusted to pH 3.9 with 11.7 g of 48% strength sulfuric acid. The resin solution had a solids content of 12.7% (1 g, 1 hour at 100 ° C.) and a viscosity at 25 ° C. of 39 mPa.s.

Example 6 (corresponds to example 8 of EP-0 349 935)

The procedure was analogous to Example 5, but with a modified amount of sodium hydroxide.

In reaction step b), 578 g of 2% sodium hydroxide solution and 416 g of water, in which 1.5 g of potassium sorbate were dissolved, were added.

Acidification was carried out with 37.5 g of 48% sulfuric acid to pH 1.75. The resin solution obtained had a solids content of 13.5% (1 g, 1 hour at 100 ° C.) and a viscosity at 25 ° C. of 40 mPa.s.

Example 7

• a) 250 g of polyamidoamine precursor solution from Example 2 (corresponding to 0.389 Val NH) and 264 g of water were placed in a three-necked flask with stirrer, thermometer and condenser and 36 g of epichlorohydrin (0.389 mol) were added with stirring. The temperature was raised to 60 ° C. in one hour and kept at this temperature. After 4 hours the Gardner viscosity was N-O. 507 g of sodium hydroxide solution (containing 6.35 g of sodium hydroxide) were added, heated to 40 ° C. and kept at this temperature. After 1.5 hours the Gardner viscosity was E-F. Then 442 g of water in which 1.5 g of potassium sorbate was dissolved were added and cooled.
• b) 733 g of the reaction product a) were immediately adjusted to pH 4.0 with 10.7 g of 48% sulfuric acid. The resin solution had a solids content of 13.0% (1 g, 1 hour 100 ° C) and a viscosity at 25 ° C of 45 mPa.s.

Example 8

733 g of the reaction product a) from Example 7 were immediately adjusted to pH 1.9 with 15.4 g of 48% strength sulfuric acid. The resin solution had a solids content of 13.2% (1 g, 1 hour at 100 ° C.) and a viscosity at 25 ° C. of 35 mPa.s.

Example 9

459 g of polyamidoamine precursor solution from Example 4 (corresponding to 0.443 eq NH) and 14 g of water were placed in a three-necked flask equipped with a stirrer, thermometer and condenser, and 53 g of epichlorohydrin (0.573 mol) were added with stirring. The temperature was raised to 63 ° C. in one hour and kept at this temperature. After 3 hours, the Gardner viscosity was F. 532 g of sodium hydroxide solution (containing 8.2 g of sodium hydroxide) were added, heated to 60 ° C. and kept at this temperature. After 3 hours the Gardner viscosity was E-F. Then 442 g of water in which 1.5 g of potassium sorbate was dissolved were added and cooled.

The reaction product was then immediately adjusted to pH 4.0 with 17.7 g of 48% sulfuric acid. The resin solution had a solids content of 13.1% (1 g, 1 hour at 100 ° C) and a viscosity at 25 ° C of 38 mPa.s.

Example 10

• a) 211 g of the polyamidoamine precursor solution from Example 3) corresponding to 0.419 Val NH) and 221 g of water were placed in a three-necked flask with a stirrer, thermometer and condenser and 50 g of epichlorohydrin (0.541 mol) were added with stirring. The temperature was raised to 63 ° C. in one hour and kept at this temperature. After 3 hours the Gardner viscosity had reached FG.
  517 g of sodium hydroxide solution (containing 15.5 g of sodium hydroxide) were added, heated to 50 ° C. and kept at this temperature. After 2 hours the Gardner viscosity was T. Then 501 g of water in which 1.5 g of potassium sorbate were dissolved were added and the mixture was cooled.
• b) 727 g of the reaction product a) were immediately adjusted to pH 4.0 with 14.6 g of 48% sulfuric acid. The resin solution had a solids content of 13.2% (1 g, 1 hour at 100 ° C.) and a viscosity at 25 ° C. of 202 mPa.s.

Production of polyamidoamine-epichlorohydrin resins (according to the invention) Example 11

459 g of polyamidoamine precursor solution from Example 4 (corresponding to 0.443 val NH) and 14 g of water were placed in a three-necked flask with a stirrer, thermometer and condenser and 53 g of epichlorohydrin (0.573 mol) were added with stirring. The mixture was heated to 62 ° C. in one hour and held for one hour, then at 65 ° C. for a further hour until the Gardner viscosity was F. 532 g of sodium hydroxide solution (containing 8.2 g of sodium hydroxide) were added, heated to 55 ° C. in the course of one hour, kept at this temperature for 40 minutes and continuously heated to 80 ° C. in the course of 3 hours until the Gardner viscosity had reached D-E.

Then 16.7 g of 45% trimethylamine solution were added and the mixture was further brought to a Gardner viscosity of EF at 80 ° C. in 30 min. The reaction product was then diluted with 442 g of water in which 1.5 g of potassium sorbate had been dissolved, cooled and adjusted to pH 4.0 with 18.7 g of 48% strength sulfuric acid. The resin solution had a solids content of 13.3% (1 g, 1 hour at 100 ° C.) and a viscosity at 25 ° C. of 41 mPa.s.

Example 12

The approach according to Example 11 was repeated with an extremely short runtime.

After a running time of approximately one hour at 75 ° C., the sodium hydroxide solution was added at a Gardner viscosity of G. After a further hour at 75 ° C. Gardner viscosity of B-C, the trimethylamine solution and after a total of 3 hours running time at 75 ° C. with a Gardner viscosity of G-H, the dilution water and the sulfuric acid were added. The resin solution had a pH of 4.0, a solids content of 13.4% (1 g, 1 hour at 100 ° C.) and a viscosity at 25 ° C. of 48 mPa.s.

Example 13

547 g of polyamidoamine precursor solution from Example 4 (corresponding to 0.528 Val NH) and 23 g of water were placed in a three-necked flask with a stirrer, thermometer and condenser, and 63 g of epichlorohydrin (0.681 mol) were added with stirring. The mixture was heated to 60 ° C. in one hour and to 64 ° C. in a further hour and held at this temperature for one hour until Gardner viscosity F and 627 g of sodium hydroxide solution (containing 9.7 g of sodium hydroxide) were added. After a 2.5 hour hold time at 73 ° C., 19.7 g of 45% trimethylamine solution were added and the mixture was further heated at 78 ° C. for one hour to a Gardner viscosity of D. The reaction product was now with 240 g of water, in which 1.5 g Potassium sorbate were dissolved, diluted, cooled and adjusted to pH 4.0 with 24.1 g of 48% sulfuric acid. The resin solution had a solids content of 16.2% (1 g, 1 hour at 100 ° C.) and a viscosity at 25 ° C. of 41 mPa.s.

Example 14

459 g of polyamidoamine precursor solution from Example 4 (corresponding to 0.443 val NH) and 14 g of water were placed in a three-necked flask with a stirrer, thermometer and condenser and 53 g of epichlorohydrin (0.573 mol) were added with stirring.

The temperature was raised to 62 ° C. in one hour and held for 2 hours until the Gardner viscosity was EF. 532 g of sodium hydroxide solution (containing 8.2 g of sodium hydroxide) were added, heated to 65 ° C. in the course of one hour and heated continuously from 65 ° C. to 75 ° C. for a further 2 hours until the Gardner viscosity had reached B to C. Then 15.3 g of N-methyl-diethanolamine were added and the mixture was further brought to a Gardner viscosity of EF at 80 ° C. in 1.5 hours. The reaction product was then diluted with 442 g of water in which 1.5 g of potassium sorbate was dissolved, cooled and adjusted to pH 4.0 with 21.5 g of 48% sulfuric acid. The resin solution had a solids content of 14.5% (1 g, 1 hour at 100 ° C.) and a viscosity at 25 ° C. of 36 mPa.s.

Example 15

The resin was prepared analogously to Example 14, instead of N-methyl-diethanolamine, 14.8 g of diethylethanolamine were used.

The reaction solution was finally adjusted to pH 4.0 with 22 g of 48% sulfuric acid.

The resin solution had a solids content of 14.3% (1 g, 1 hour at 100 ° C.) and a viscosity at 25 ° C. of 26 mPa.s.

Example 16

223 g of polyamidoamine precursor solution from Example 3 (corresponding to 0.443 val NH) and 250 g of water were placed in a three-necked flask with a stirrer, thermometer and condenser and 53 g of epichlorohydrin (0.573 mol) were added with stirring. The mixture was heated to 60 ° C. in one hour and then the temperature was raised to 65 ° C. in the course of 2.5 hours until the Gardner viscosity was E-F.

532 g of sodium hydroxide solution (containing 8.2 g of sodium hydroxide) were added, the mixture was heated to 55 ° C. in the course of one hour and heated continuously from 55 ° C. to 80 ° C. for another 2 hours until the Gardner viscosity had reached C. Then 11.2 g of N, N-dimethylisopropylamine were added and the mixture was further brought to a Gardner viscosity of C at 80 ° C. in 1.5 hours.

The reaction product was then diluted with 442 g of water in which 1.5 g of potassium sorbate had been dissolved, cooled and adjusted to pH 4.0 with 21.2 g of 48% strength sulfuric acid. The resin solution had a solids content of 13.8% (1 g, 1 hour at 100 ° C.) and a viscosity at 25 ° C. of 24 mPa.s.

Example 17

The resin was prepared analogously to Example 16, instead of N, N-dimethylisopropylamine, 13.0 g of diisopropylamine were used.

The reaction solution was finally adjusted to pH 4.0 with 22.4 g of 48% sulfuric acid.

The resin solution had a solids content of 14.0% (1 g, 1 hour at 100 ° C.) and a viscosity of 17 mPa.s.

Paper handling

To a 2% suspension of bleached sulfite pulp with a freeness of 42 to 43 ° C. Schopper-Riegler, the aqueous resin solutions from Examples 5 to 17 were added in an amount of 1% solid resin to pulp with vigorous stirring.

After a mounting time of at least 2 minutes, two sheets of paper from approx. 320 cm² area with a basis weight of 100 g / m², dried on a steam-heated cylinder for 5 minutes at 100 ° C and post-cured in a drying cabinet at 120 ° C for 10 minutes. After an air-conditioning period of 24 hours at 20 ° C and 65% relative humidity, the wet strength in Newtons (N) was measured from test strips of the paper in accordance with leaflet V / 12/57 of the ZELL-CHEMING association. The paper obtained in this way had a wet strength which was considerably higher than that of paper which was produced from the same bleached sulfite pulp without the addition of the aqueous solutions of the products used according to the invention under the same test conditions.

The wet strengths in Newtons (N) are given in relative%, based on comparative product 9 = 100%, in Table 1.

Examples 5 to 10 are comparisons to the prior art (EP-0 349 935).

As the comparative examples show, high storage stability at a desired pH of about 4 can only be obtained if the content of organically bound chlorine is also relatively high (Examples 5 and 9). However, high storage stability and simultaneous deposition of the chlorine content is only possible by an undesirably large drop in the pH (Examples 6 and 8). A further reduction in the chlorine content at a relatively high pH is possible, but leads to loss the storage stability (Examples 7 and 10). Examples 11 to 17, on the other hand, show that by treating the resins with an organic amine, all three parameters can be adjusted to optimum values at the same time.

Claims (10)

Aqueous resin solution containing as the resin a water-dilutable polyamidoamine-epichlorohydrin resin (A) obtained by a) reaction of a water-dilutable, basic polyamidoamine (B) with epichlorohydrin, b) reaction of the resin thus obtained with an inorganic base and with a water-soluble organic mono- or polyamine or with ammonia or mixtures thereof and c) adding an acid so that a pH of 1 to 7 is reached. Resin solution according to claim 1, characterized in that the pH is between 1 and 7. Resin solution according to at least one of Claims 1 to 2, characterized in that the content of organically bound chlorine in the resin (A) is 0.001 to 2.5% by weight. Resin solution according to at least one of Claims 1 to 3, characterized in that the resin (A) content is between 8 and 25% by weight. Resin solution according to at least one of Claims 1 to 4, characterized in that the amount of inorganic base is 0.1 to 1.0 mol per mol of epichlorohydrin used. Resin solution according to claim 5, characterized in that sodium or potassium hydroxide is used as the base. Resin solution according to at least one of claims 1 to 6, characterized in that the polyamidoamine-epichlorohydrin resin is reacted with a mono- or polyamine or with ammonia or mixtures thereof in amounts such that 0.01 to 2 val basic amino groups are present per mole of epichlorohydrin are. Resin solution according to at least one of Claims 1 to 7, characterized in that compounds of the formulas are used as mono- or polyamines



NR₁R₂R₃ or R₄R₅N (-R-NR₈) _n -R-NR₆R₇



are used in which
R is an aliphatic, cycloaliphatic or araliphatic alkylene or hydroxyalkylene radical having 1 to 300 carbon atoms, which can be interrupted by heteroatoms such as oxygen and sulfur, and R₁, R₂, R₃, R₄, R₅, R₆, R₇ independently of one another hydrogen or an aliphatic , Cycloaliphatic or araliphatic alkyl or hydroxylalkyl radical having 1 to 20 carbon atoms, which can be interrupted by heteroatoms such as oxygen and sulfur, and n is an integer from 0 to 10. Resin solution according to at least one of Claims 1 to 7, characterized in that polyamidoamines are used as polyamines. Use of the aqueous resin solution according to at least one of Claims 1 to 7 as an auxiliary in the paper industry, in particular for increasing the wet strength of paper.